Preparation of synthetic resins from thiazoles



Patented Mar. 19, 1946 V v r ,UNITED STATES PATENT OFFICE PREPARATION OF SYNTHETIC RESIN S FROM THIAZOLES No Drawing. Application August 29, 1942, Serial No. 456,687

8 Claims. (Cl. 260-29) The invention relates to the preparation of the group-consisting of H, methyl, ethyl, n-propyl, novel thermosetting synthetic resins by reaction i opropy ph l and n y B 18 8 bivalent or an aldehyde with a partl'cluar type of thiazole. radical selected from the roup conslst ns of Nearly all the known resins formed by the ree y ene, a o y phenylene havins not more action 01' formaldehyd with various compounds 5 than two alkoxy groups each containing not more are without practical value because of undesirable than two carbon atoms (CH2)n-, p ysical properties. Most of them are thermoplastic or so slowly thermosetting that they may GOO be regarded for all practical purposes as thermoplasfim. and I Formaldehyde reacts with certain nitrogenous I compounds, such as urea, to form thermosetting l O CH CH 0) resins, but the resins so produced hav one outastanding disadvantage, which is relatively low Y wat r i ta n :is an integer not greater than 12; and a is The principal object of the invention is the an integer n t er h preparation of novel thermosetting resins having The thiazoles that are reacted with aldehydes superior water resistance by e t of o in accordance with the invention toproduce novel hydes with nitrogenous compound More spe resins may be prepared by reacting thiourea with c bjects and advantages are apparent from a dihalo diketone. Each molecule or the dihalo the description, which discloses and i t t diketone reacts with 2 molecules of thiourea to the invention andisnot intended to impose'limiproduce the hydrohalide of a bis-2-aminotations upon th claims. thiazolyl' compound, which may be treated with a Thiazoles have not been known hereto-fore to base in order to set free the bis-Z-amino-thiazolyl produce thermosetting re in by reaction with compound. If a halogen atom is attached to the aldehydes. The present inv nt n i based upon carbon atom inside of the carbon atom oiflone the discovery that thiazoles of a certain type of the ar onyl groups of the diketone, th n the react with aldehydes to form r i th t are reaction with one molecule of thiourea which fusible, insoluble and heat resistant and have outtakes place at t carbon ms P c a standing water-resistance. The formation of so 2-amin0-5-thiaZ0ly1 group f a l en M thermosetting resins by reaction of thiazoles of is ta d to the a o a m ou sid of the this type with aldehydes higher than formaldecarbon atom of one of the carbonyl 810 19 of yde-is extraordinary because urea, and other the diketone, then the reaction with one molecule nitrogenous-compounds in general that react with of thiourea which takes place at the two carbon formaldehyde to form thermosettingresins, proas atoms prod s a -mino-4-thiazolyl r up.

duce only thermoplastic resins by reaction with Resins that h W y varie pr perties and higher aldehydes. are therefore suitable for various uses may be Bls-2-amino-4-thiazoly1 prepared in accordance with the invention, be-

- cause a large variety of dihalo diketones may cn=cc=cn 40 be used for the reaction with thiourea to give A 1; g various thiaz'oles that may be reacted with aldehydes to produce resins.

c Certainl dihalo diketones for use in such a mi. NH, reaction with thiourea may be prepared by carryin out a Friedel-Crafts reaction between an does not form thermosetting resins by reaction a o atic compound and an acyl halide.

with aldehydes-l r.- h s n en For example, thiazoles for reaction with aldecovered that thcrmos t n resins having the, ehydes in accordance with the invention may be i e Pr p rties stated above are produced by prepared by carrying outaFriedel-Crafts reaction reaction of aldehydes with substances having between substance having th gon ral formula the general formula Rl-A1BA2-R2, in Y which A1 and A2 are bivalent radicals having I 2 the formula CE-C -C=C 'R x A -"";iI.-. in which Xi'and Xi are'selected fromthe group 0 a consisting ofCi and Br, and R is selectedirom the groupcohsisting of H,. methyl,'ethy1,'n-

propyl, isopropyl, phenyl and 'ben'zyl, and a sub- R1 and R: are monovalent radicals selected from stance selected from the group consisting of a solution of an benzenefag allroxy benzene having not more than two alkoxy' 'groups each containingnot more than two carbon atoms, diphenyl ether and substances having the general formula Oo-wm-cm-oaO are chloroandieither diphenyl ether C or the diphenyl-ether of ethylene glycol or the dlphenyl ether of a polyethylene ghrcol containing not more than 6 ethylene groups Other thiazoles for use in practicing, the invention may be produced by carrying out a Friedel-Crafts reaction between 1 mol of the dihalideof a d ibasic straight chain aliphatic acid containing from 3 to 14 methylene groups between the acid halide groups. and 2 mols of benzene, and then halogenating the inter-most methylene group's or the resultingdiketone to produce a dihalo diketone which can be conbis-thiazolyl compound by reaction verted. to a. with thiourea.

Still other thiazoles for use in practicing the invention may be prepared by reacting the di- I chloride of a straight chain aliphatic acid containing 1 to 12 methylene groups with diazomethane, reacting the resulting bis-diazo-dlketone with hydrogen chloride, and reacting thiourea with the dichloro diketone so obtained.

Inaccordance with the i of. the class described may be reacted with formaldehyde, acetaldehyde, propionaldehyde, nbutyraldehyde, isobutyraldehyde, crotonaldehyde, furfuraldehyde, or a polymer thereof, such as paraformaldehyde. Preferably, it is reacted with aldehyde in water, in an organic solventrsuch as alcohol, or in a liquid containing both water'and an organic solvent. If an organic solvent; such as ethyl, methyl, propyl or n-butyl .alcohol,:or the monomethyl or monoethyl ether of ethylene glycol is employed, the solution of invention, a thiazole an intermediate reaction product that is obtained.-

.is suitable'for use in lacquers, and the reaction may be performed in an autoclave if desired to secure a reaction temperature above the boiling point of the solvent. Some thiazoles of the class described are insoluble in water, but arr-organic solvent may be used it desired for ch thiazoles with an aldehyde.

tion is strongly acid,'a,

INTERMEDIATE Rmcrron Paonuc'r reaction with the thiazole, the solution is preferably about neutral at the start of the reaction. Since commercial aqueous formaldehyde solubase is preferably added to bring the initial pH of the reaction solution to the desired value. Any desired base may be employed. If the thiazole used is insoluble in water, an organic solvent may be added to the aqueous formaldehyde solution to expedite the ing the reaction,

reaction.

- From less than 1 mol to 4 or more moles of an aldehyde may be used for the reaction with each mol of the thiazole. Because of the complexity.

of the molecules of the reaction product, the proportion of the aldehyde actually reacting with each mol ofthe thiazole can vary from 1 mol to as many as 4 mols. An excess of either reactant may be used if desired, although an unreacteduncombinable excessof one of the reactants is not usually desirable in the final product. The preferred proportion is from about 1% to 2% mols of the aldehyde for each mol of the thiazole. g

The reaction proceeds at ordinary temperabut is expedited by heating. An intermediate reaction product may be prepared by carrying the reaction of the aldehyde and thiazole only to its earliest stage, for example, the stage at which the reacting ingredients have just dissolved to iorm a solution, or the reaction or condensation a stage (Short of the final, infusible resinous stage) at which the product may still be called an intermediate reaction product. By thus advancit is possible to obtain an interi. mediate reaction product that is insoluble but still fusible.

Some of the thiazoles described form only water-insoluble reaction products by reaction with formaldehyde or other aldehydes, but a stable solution of an intermediate reaction z product in an organic solvent can ordinarily be prepared.

For many purposes it is convenient to allow Q the soluble type of intermediate reaction product ture of plywood,

, vacuum drum-drying. It

the reaction to remain in the form of a solution. Such a solution, after the addition of any desired ingredients, may be used as a binder in the production of impregnated or laminated products, as an adhesive for applications, such as the manufacas a dressing or creaseprooflng agent for textiles, as an ingredient for lacquers or coating compositions, as a flameproofing agent for wood, and as a. composition to be converted into a foam that can be hardened to produce aninsulating material.

An intermediate reaction product may be obtained in dry form from a solution by evaporating or diluting it, to adjust its concentration then spray-drying or is usually more convenient to ship or store an. intermediate reaction product in dry form than in the form of a solution. Various ingredients, such as fillers, pigments and hardening catalysts may be mixed with a dry intermediate reaction product so that a coating compound, adhesive, binder or impreghating agent of the desired composition maybe obtained by simply adding water or other solvent to the dry mixture.

The product is most stable in storage when it is substantially neutral. Thus, it is desirable to the proper value, and

may be carried to any further.

' stantially neutral so long as the reaction vessel is 4 hours. Hydrogen assaece action product before spray-drying or vacuum drum-drying.

An acid catalyst ma be used in hardening or converting .the intermediate reaction product into an infusible resin. Since the action or the catalyst is due solely to its acidity, any acid substance, such as an inorganic acid, an organic acid, or an acid salt such as an ammonium salt of a strong inorganic acid, may be used as the catalyst. The acidity may be furnished by mere addition of an acid substance to the intermediate reaction product, but acidity tocatalyze the conversion of the intermediate reaction product to an infusible resin is preferably provided by incorporating a latent acid catalyst with the intermediate reaction product. A latent acid catalyst is a substance which after being added to the-intermediate reaction product, remains subthe reaction product is. stored at ordinary temperatures, but decomposes or reacts to generate acidity whenthe intermediate reaction product is heate. in the operation of converting it into an infusible resin. The degree of acidity employed during the hardening of the intermediate reaction product is simply that acidity which causesthe intermediate aldehyde in a 37 per cent aqueous solution whose pH has initially been adjusted to a value from about 6.5 to about 7.5, e. g. 6.8, are reacted to form an intermediate reaction product. If the reaction is carried out by heating at 90 to 120 C. for a few minutes, the thiazole does not dissolve but is converted by reaction with the formaldehyde to an amorphous semi-solid product that is transformed into an infusible resin either by heating or by acidification. An alkali also acts as a catalyst to cause conversion of this intermediate reaction product to an infusible resin.

.since such conversion is produced at ordinary temperatures by addition of an alkali to the in termediate reaction product. Any alkaline material may be employed. Preferably. a solution is prepared by warming the thiazole with ethylene glycol monomethyl other before the formaldehyde solution is added. The resulting 40 per cent solution' of an brought to a pH of about 6 by addition of maleic reaction product to harden at the desired rate.

Example 1 then added slowly to a well stirred suspension of 2 mols of cc. of carbondisulfide contained in a vessel surrounded by ice. After the addition of all the reactants, a reddish oil is present. In order to keep the oil mobile enough for continued stirring.

surrounded with lukewarm water while the reaction is continued for chloride is liberated. The carbon disuli'ide is then poured oif and the reddish oil is decomposed by addition of water containing sufiicient hydrochloric acid to prevent the aluminum chloride from hydrolyzing to aluminum hydroxide. The resulting precipitate is separated and may be purified by crystallization from alcohol to produce a 50 per cent yield of p,p'- bis-chloroacetyl-diphenyl ether, which is a nearly white solid melting at 99-102 C. The foregoing step is a" typical Friedel-Crafts reaction. 150 grams of this substance, 25o grams of thiourea, and 750 cc. of water containing 4 cc. of conce trated hydrochloric acid are heated on a water bath until precipitation of the resulting hydrochloride has been completed.- The precipitate is anhydrous aluminum chloride in 850 separated and then dissolved in 9 liters of boiling water. After filtration, the hot solution is neutralized' with a solution of sodium bicarbonate. The solid product is filtered, washed, and then recrystallized from the monomethylether of sistency for useas an adhesive. Birch plies be coated on one side with about 15 to 16 of the adhesive per square foot, allowed to 1 hour, assembled and then pressed at 250 F. for 15 minutes. The adhesive bond in the resulting plywood has excellent water-resistance.

Example 2 may grams 18 grams of the thiazole prepared in accordance with Example 1, 20 cc. of butyraldehyde, or an equivalent amount of crotonaldehyde or furfuraldehyde, 1 cc. of a 10 per cent aqueous sodium hydroxide solution and cc. of ethylene glycol monoethyl ether are heated to produce a viscous solution. The reaction product in this solution is converted to an infusible resin by I slightly acidifying and then heating.

Example iii grams of sodium hydroxide'and 94 grams ofphenol are dissolved in cc. of water. After the addition of 100 cc. of alcohol and 94 grams of ethylene dibromide, the solution is refluxed for 16 hours, filtered and then cooled. The solid dipheliyl ether of ethylene glycol that separates,

- precipitation of aluminum hydroxide.- The diethylene g ycol to give the p.p'-bis-2-amino-4- thiazolyl diphenyl ether EQ S N i i I I I O/ NH: F IHg which melts at 246-248 C. The over-all yield of this product based on the amount of diphenyl chlorodiketone which separates as a precipitate melts at l55-165 0. Thirty grams of this substance and 16.5 grams of thiourea ar dissolved in n-butanol and heated at boiling temperature until precipitation of the resulting hydrochloride has been completed. The precipitate is dissolved in water and the aqueous solution is neutralized with sodium bicarbonate and then boiled to cause precipitation of the bis-2-amino-e-thiazo1y1 diphenyl ether of ethylene glycol, which has a melt.- ing point of 255-260 C. The product may be treated in the same manner as the thiazole in Example 1 to produce an intermediate reaction pact with formaldehyde. 3

intermediate reaction product is.

dry for substance and 40 cc. of chloracetyl chloride is Erample 4 aluminum chloride in 120 cc. 'of carbon disulfide.

add ethylene glycol monomethyl ether unless it In the next step of the reaction, 16.5 grams of dichloro diketone and grams of thiourea are employed. The thiazole is a bis-2-amino-4- thiazolyl diphenyl ether of diethylene glycol having a melting point of 1781'l9 Example 5 The procedureof Example 3 is followed except that 94 grams of the p,c'-di-chlorethyl ether of ethylene glycol are used instead of the 94 grams of ethylene dibromide. At the end of the 16 hours oi refluxing in the first step,sodium chloride has separated out and the supernatant liquid is decanted from the sodium chloride. After the decanted liquid has been allowed to cool, an oil layer can be separated. Drying this oil by means of calcium chloride followed by distillation gives as the .distillate the diphenyl ether of triethylene glycol, which boils at 240 C. under a pressure of 15 mm. of mercury and has a melting point 0! 42 C. The procedure of Example 3 is then continued using a mixture of grams of this substance with 22 cc. of chloracetyl chloride and a suspension of grams of anhydrous aluminum chloride in 200 cc. of carbon disulflde. In' the next step of the reaction, 30 grams of the dichloro diketcneand about 20 grams of thiourea are employed. 'The thiazole is a bis-2-amino-4- thiazolyl diphenyl ether of triethylene glycol which sinters at 150 C. and melts at 165 C.

Example 6 A mixture of 15 grams of anisole and 90 grams of bromo-acetyl bromide is added slowly to. a Well-stirred suspension of 40 grams of anhydrous aluminum'chloride in 230 grams of carbon disulfide contained in a vessel surrounded by ice. After this addition, the reaction vessel is surrounded with luke-warm water while the reaction-is continued for 4 hours. The resulting solution together with sumcient hydrochloric acid to prevent the precipitation of aluminum hydroxide is then poured on ice. The non-aqueous product is separated from th ice and extracted with diethyl ether and the ether extract is evaporated to aresidue that is still liquid. Then after the addition of 70 cc. of ethyl alcohol, the product is cooled to crystallize the bis-bromacetyl anisole, which has a melting point of 76-80 C.

A solution of -3.3 grams of this substance and 1.4 grams of thiourea in 30 cc.- of 60 per cent ethyl alcohol is heated on a water oath for 2 hours. After cooling, a precipitate of the hydrochloride can be separated. The precipitate is dissolved in 40 cc. of hot water containing. 1.5 grams of sodium bicarbonate to cause precipitation of the bis-2-amino-4-thiazolyl anisole which has a melting point of 205-208 C. The thiazole so prepared may be reacted with formaldehyde in the same manner as the thiazole prepared in accordance with Example 1-. In this case, however, theintermediate reaction product is soluble in water so that it is not necessary to is desired to prepare a stable solution.

Example 7 ice. the addition requiring about'30 minutes.

The surrounding ice is then removed and stirrin is continued for 1 hour and 45 minutes until the contents of the vessel has substantially attained room temperature. The contents of the vessel is then poured upon a mixture of 600 grams of ice and 122 cc. of concentrated hydrochloric acid. Sufflcient additional benzene is then added to cause all of the white precipitate to dissolve and the benzene solution isseparated. After the benzene solution has been washed with a dilute solution of sodium carbonate, the benzene solution is dehydrated by means of calcium chloride and the benzene is distilled off. The residue of alpha,omega-dibenzoyl octane is purified by recrystallization from alcohol. Forty grams of the product and cc. of carbon tetrachloride are heated under reflux andabout 40 grams of bromine are added one drop at a time, until no further absorption of bromine occurs. Distillation is then carried out to produce a concentrated solution, which is cooled to cause crystallization. The crystalline product, which is purified by washing with a petroleum ligroin,

melts at 83 C. and has the structural formula l NH: 1 3:

Example 8 Sixteen grams of cz-ChlOl'Dl'OplOIlYl chloride are mixed with 10 grams of diphenyl ether. The mixture is then added to a well-stirred suspension of 15 grams of anhydrous aluminum. chloride in 75 cc. of carbon disulfide contained in a vessel surrounded by ice. After this addition, the reaction vessel is surrounded with luke-warm water while the reaction is continued for 4 hours. The carbon disulflde is decanted and the oil that remains is decomposed by addition of water containing sufliclent hydrochloric acid to prevent the precipitation of aluminum hydroxide. The resulting product which separates as a precipitate is 9.9-bis-alpha-chloro-propionyldiphenyl assess-1 ILH: I The product may be treated in the same manner dichloride, an equivalent amount or sebacyi dichloride is employed. The thiazole in this case is 1,8-bis-2-amino-4-thiazolyl octane, having a melting point of 180 C. The over-all yield of this compound is 67 per cent.

I PRODUCTION 01* ARTICLES OF INFUSIBLE RESIN? Fillers, plasticizers, hot plate lubricants, opacifiers, dyestuii's, pigments and other coloring matter may be incorporated with the intermediate reaction product to produce a suitable moldin composition. In the preferred method of preparing a molding composition, the filler is impregnated witha solution of a soluble intermediate reaction product, and the solvent is then removed.

If fibrous cellulosic material in the form of 7 paper pulp, wood flour or the like is employed as as the thiazoleof Example 1 to produce an intermediate reaction product with formaldehyde.

Example 9 A solution of 65 grams of adipyl dichloride in 250 cc. of dry 'diethyl ether is added in portions to 2 liters of a dry diethyl ethersoiution of diazo methane prepared from about 180 grams of nitroso methyl urea. The tetramethylene bis diazo-dimethyl diketone that precipitates is tates is filtered oil. One moi of this product is 3 reacted with 2 mols of thiourea by heating on a water bath in solution, with 60 per cent ethyl alcohol as the solvent. The precipitated hydrochloride is separated and then treated with an aqueous solution of sodium bicarbonate to produce a 45 per cent over-all yield of the 1,4-bis-2- aminoi-thiazolyl butane, having a melting point of 216 C.

The thiazole so prepared may be reacted with formaldehyde in the same manner as the thiazole prepared in accordance with Example'l. In this case, however, the intermediate reaction product is soluble in water so that it is not necessary to add ethylene glycol monomethyl ether unless it is desired to prepare a stable solution.

Example 10 substantially all of the water has been removed.

the solution is evaporated to a final weight of about 90 grams. The resulting coating composition when poured out in a him and baked for 30 minutes at 105 C. produces a very hard transparent infuslble film.

Example 11 The procedure of Example 9 is carried out except that instead oi the 65 grams of adipyl the filler, a solution of the intermediate reaction" product used for impregnating th cellulosic material is preferably rendered acid (pH ofabout 4 to about 6). Heat may be used to facilitate the drying of the impregnated cellulose or other filler. 0! course, the drying temperature should not besumcient to render the molding compo sition infusible. After the water or other solvent has been removed, the dry product may be ground in a ball mill to produce a homogeneous powder; and modifiers, such as plasticizers, lubricants and pigments, may be incorporated in the grinding operation. If desired, the powder may be compressed into blanks or preforms of the proper sizes for use in various molds. The molding composition may be employed in the usual manner for the productionof molded articles by compressing it in a closed mold at a pressure of 1 to 4 tons per square inch of projected area and a temperature between 100 C. and.200 C., preferabiy about Mil- 0., for a period'of 1 to 5 minutes.

Articles oi iniusibie resin embodying the invention may be produced by methods other than preparing and hot-pressing a molding composition, for example, by casting in open molds and baking. In any case, if no filler is used, transparent articles can be produced. 7

en the synthetic resins of the present invention are utilized, the intermediate reaction products that have been described can be incorporated'in a great variety 01' other resins or potential resins such as urea-formaldehyde resins and'phenol formaldehyde resins. Also, reaction products of an aldehyde or .a mixture of aidehydes with a mixture of the thiazoles with one another or with other substances, such as urea and thiourea, can be produced. The intermediate reaction products in the resulting compo sitions may then be converted into the infusible resins, and a blend or copolymer of different resins may thus be obtained.

Example 12 radical selected phenylene,

- than two carbon atoms.

Ec'ample 13 ambs-cellulose, 2 grams of zinc stearate, 40 grams of a 8'7 per cent aqueous solution of formaldehyde and 1% cc. of a 10 per cent aqueous sodium hydroxide solution are kneaded in a. Banbury mixer while slightly warm to produce a homogeneous mass. The material'is dried for about 10 minutes at 185' F. and is then ground in a ball mill to produce a molding powder. Articles molded from the resulting composition are very fast curing in the mold and have excellent waterresistance.

Various embodiments of the invention may be devised to meet various requirements.

Having described the invention, I claim:

1. A method of producing a synthetic resin that comprises reacting a substance, selected irom the group consisting of formaldehyde, acetaidehyde. propionaldehyde, n-buty'raldehyde, isohyde, withia substance having the general formula R1-AiB-Az-R2, in which A1 and are bivalent radicals having the formula R: and R: are the group consisting of H. methyl, ethyl, n-propyl, isopropyl, phenyl and benzyl; B is a bivalent radical selected from the group consisting of phenylene, aikoxy phenylene having not more than two alkoxy groups each containing not more than two carbon atoms, -,-(CH:) 1-,

and

' OO-(CHr-Cfir-OLO n is an integer not greater than 12; and a: is an efler not greater than 6. I

2. A method of producing an intermediate reaction product capable or conversion into an n is an integer not greater than 12; and a; is an integer not greater than 6. a

3. A reaction product or an aldehyde selected from the group consisting of formaldehyde, acet- 5 aldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, crotonaldehyde, and furiuraldehyde, with a substance having the general formula R1-A1-BA2Ra, in which A1 and A: are bivalent radicals having the formula N i \C/ 15 R1 and R2 are monovalent radicals selected from butyraldehyde, crontonaldehyde, and furfuraldemonovalent radicals selected from infuslbie resin that comprises reacting formaldehyde with a substance having the general formula Ri-Ai-B-Aa-Ra, in which A1 and A2 are bivalent radicals having the formula R: are monovalent radicals selected from i N i:

R1 and the group consisting of H, methyl, ethyl, n-propyl',

and benzyl; B is a bivalent from the group consisting of alkoxy phenylene having not more than two alkoxy groups each containing not more (CH2)n-.

isopropyl, phenyl the group consisting of H, methyl, ethyl, n-propyl, isopropyl, phenyl and benzyl; B is a bivalent radical selected from the group consisting of phenylene, alkoxy phenylene having not more than two aliroxy groups each containing not more than two carbon atoms,-(CH:)s--. 4

nd I

'QO-(CIIi-OHa-MO n is an integer-not greater than 12: and a: is an integer not greater than 6.

4. An intermediate reaction product of formaldehyde with a substance having the general formula R1-AiBAa-R:. in which A1 and A: are bivalent radicals having the fromula the group consisting of H, methyl, ethyl, n-propyl, isopropyl, phenyl and benzyl; B is a bivalent radical selected fromgthe group consisting or phe'nylene, alkoxy phenylene having not more a than two alk'ozy groups each containing not more than two carbon atoms, (CH:) a--,

n is an integer not greater than 1.2: and sis an 5. An intermediate reaction product or formaldehyde with a bis-2-amino-4-thiaz0lyl diphenyl ether of ethylene glycol, capable of conversion intoaninfusible resin. a 6. An intermediate reac ion product of formaldehyde with a bis-2-amino-4-thiaz0ly1 diphenyl ether of a polyethylene glycol containingfnot more than six ethylene groups, capable of conversioninto an iniusible resin. ei,- '7. An intermediate reaction product ofform aldehyde with p,p-bis-2-amino-4-thiazoiyl diphenyl ether,1capable of conversion into an infusi-ble resin.

"8. An organic solution comprising anintermediate reaction product of an aldehyde selected from the group consisting of iormaldehyde, acetaldehyde, propionaldehyde. n-butyraldehyde. isobutyraldehyde, crotonaldehyde, and furfuraide hyrie, with a substance having the general foraseaaea. 7'

male R1-A1--B-Aa-R:, in which A1 and A: than two alkoxy groups each containing notimore are bivalentradicais having the formula than two carbon atoms, -(CH=) 1-,

R1 and R2 are monovaient radicals selected from 1 n is an inte er not gr at r th n 1 and a: is an the group consisting of H,methy1,ethy1.n-Droi yi. o integer not greater than 6, capable of converisopropyl, phenyl and benzyl; B is a bivalent sion into an intusibie resin, and an alcoholic radical selected' from the group consisting of solvent for such intermediate reaction product. phenylene,'alkoxy phenylene having not more JOHN KENSON SIMONS. 

